Detergent washing composition

ABSTRACT

A DETERGENT WASHING COMPOSITION CONTAINING AN ALKALI SALT OF A HYDROPEROXIDE AND A WATER-SOLUBLE SYNTHETIC ORGANIC SURFACE ACTIVE AGENT.

ABSTRACT OF THE DISCLOSURE A detergent washing composition containing an alkali salt of a hydroperoxide and a water-soluble synthetic organic surface active agent.

This invention relates to detergent washing compositions for cleaning soiled laundry at the boil. The composition is a powdery solid.

Until now, oxidazable soils on laundry have generally been cleaned at the boil with detergent washing compositions containing sodium perborate.

In order to be effective for washing laundry containing oxidizable stains, the peroxide compound in the detergent washing composition should have certain characteristics including:

It must be soluble in water, since water insolubility would lead to nonuniform cleaning leaving spots or streaks;

Preferably it should be solid, since use of liquids in solid powdery compositions is extremely difficult;

It must be stable in storage conditions to which the compositions are subjected before sale and use.

In the past organic peroxides have not been desirable for cleaning soiled laundry because of lack of stability in the composition which results in poor cleaning efficiency. Further, many are not solid and/or have little solubility in water.

It is an advantage of this invention that a washing detergent composition is provided which contains an organic peroxide' which is water soluble, solid and has good storage stability and cleaning efficiency at the boil.

Other advantages will be apparent from consideration of the specification.

In accordance with certain of its aspects, this invention relates to a stable, substantially dry, washing detergent composition for cleaning soiled laundry at the boil which comprises a water-soluble synthetic organic surface active agent and an alkali salt of a hydroperoxide having the formula:

in which R R and R are each hydrogen or a hydrocarbon radical, R R and R not being all simultaneously hydrogen and two of R R, and R capable of being part of the same cyclic hydrocarbon group and M is an alkali metal, such as sodium or potassium or ammonium.

The nature of hydrocarbon radicals R R and R is not critical and they can be therefore chosen among the straight or branched chain alkyl radicals, especially alkyl radicals having 1 to 12 carbon atoms, the aryl alkyl radicals, the cycloalkyl, alkyl-c'ycloalkyl and arylcycloalkyl radicals, the unsaturated homologues of these alkyl and cycloalkyl radicals, and the aromatic radicals, especially phenyl, alkylphenyl, naphthyl, alkylnaphthyl and antracenyl.

These hydrocarbon radicals can be by other means substituted by different heteroatoms or groups of heteroatoms, such as for example halogen atoms, hydroxyl groups, nitrates, sulfonyls, ethers, carboxylic acids or esters of carboxylic acids.

3,746,645 Patented July 17, 1973 As nonlimitative examples, utilizable according to the invention can be therefore cited salts of sodium, potassium or ammonium of hydroperoxides of:

tertiary amyl tertiary butyl propyl dimethyl methane propyl diethyl methane propyl butyl ethyl methane propyl ethyl ethane propyl butyl ethane octyl decyl undecyl 2-ethyl-hexyl pentamethyl ethyl l-methyl cyclohexyl l-ethyl cyclohexyl phenyl cyclohexyl phenyl cyclohexane methyl cyclopentane methyl cyclohexane indanyl pinene p-methane benzyl cumene sulfocumene butyl benzene dibutyl benzene p-cymene t-butyl dimethyl benzene Z-phenyl propyl diphenyl methane di-isopropyl benzene isopropyl chlorobenzene isopropyl naphthalene, and phenylpropyl methane As other examples can be also cited salts of sodium, potassium, and ammonium of hydroperoxides obtained by auto-oxidation of tetralin, of octahydroanthracene, etc.

The non-salified hydroperoxides are not utilizable in washing compositions, for generally they are liquids, insoluble in water and often present a strong odor which is difficult to conceal. It has been proposed to condense these hydroperoxides with sultones, such as popane sultone, or alkylene oxides, such as ethylene oxide, however, the resulting products possess too much stability and do not efficiently release oxygen to permit effective cleaning of soiled laundry.

On the contrary the alkali salts of hydroperoxides utilized in the instant invention are soluble in water, are without rehibitory odor and produce effective cleaning of soiled laundry. In addition, they are produced from hydroperoxides in accordance with known procedures at very low cost compared to the cost of condensing with sultones or alkylene oxides.

The alkali salt of hydroperoxide is introduced into the composition in such amount that the amount of active oxygen in the powder is 0.2 to 4%, which corresponds to usual doses found in classical compositions of a persalt base. The content by weight of the composition in salt of hydroperoxide thus varies in function of the molecular weight of the latter. As a general rule this content is however from 0.5 to 10%.

The surface active agent which may be employed may be any commonly used compound having surface active or detergent properties. Most preferable are those watersoluble surface active compounds having anionic or nonionic properties. Anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably 12 to 22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group on a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate; sulfated aliphatic alcohols such as sodium lauryl and hexadecyl sulfates, triethanolamine lauryl sulfate, and sodium oleyl sulfate; sulfated alcohol ethers, such as lauryl, tridecyl, or tetradecyl sulfates including 2-4 ethylene oxide moieties; sulfated and sulfonated fatty oils, acids or esters such as the sodium salts of sulfonated castor oil and sulfated red oil; sulfated hydroxyamides such as sulfated hydroxylethyl lauramide; sodium salt of lauryl sulfoacetate; sodium salt of dioctyl sulfosuccinate; and the sodium salt of oleyl methyl tauride.

Other anionic surface active agents which may be employed in the practice of this invention include olefin sulfonates, typically containing 8-25 carbon atoms.

Also included within the ambit of the invention are the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monolyceride monosulfate, tallow diglyceride monosulfate; and the hydroxy sulfonated higher fatty acid esters such as the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic acid ester of isethionic acid.

Nonionic surface active agents are those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido, or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannitan monopalrnitate and the condensation products of polypropylene glycol with ethylene oxide.

Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents, there may be noted the diamines such as those of the type RNHCfl-LNH; where R is an alkyl group of 12 to 22 carbon atoms, such as N-aminoethyl stearyl amine and N-aminoethylmyristyl amine; amide-linked amines such as those of the type R'CONHC I-LNH wherein R is an alkyl group of about 12 to 18 carbon atoms, such as N- amino ethyl-stearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including such 1 to 3 carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate and monosulfate. Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, methyl-ethyl-dilauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.

The surface active compounds which are used in the most preferred aspects of this invention are those having anionic or nonionic properties. The most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and mangesium) salts of the higher alkyl benzene sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein.

The surface active agent is typically present in amount of about 4-95 by weight of the detergent composition, preferably about 4-40%.

In addition to the materials described above, the detergent composition of the invention may include a builder for the detergent. The builder may be any of the watersoluble inorganic builder salts commonly known in the art, or it may be a water-soluble organic sequestering agent such as sodium nitrilotriacetate, or mixtures thereof.

The water-soluble inorganic builder salt may be suitable alkali metal, alkaline earth metal, or heavy metal salt or combinations thereof. Ammonium or an ethanol-ammonium salt in a suitable amount may be added also, but generally used are the sodium and potassium phosphates, silicates, carbonates, bicarbonates, borates, sulfates, and chlorides. Particularly preferred builder salts are polyphosphates, silicates and borates.

In the water-soluble inorganic builder salt mixtures used in the detergent compositions, it is often preferred to have present a mixture of sodium tripolyphosphate and sodium or potassium bicarbonate, such as a combination or mixture of salts wherein the bicarbonate to tripolyphosphate ratio is selected from the range of about 1:1 to about 3:1.

Both Phase I and Phase II sodium tripolyphosphate and mixtures thereof may be successfully used in the compositions. The usual commercial tripolyphosphate consists mainly of the Phase II material. The commercial tripolyphosphate material is usually essentially tripolyphosphate, e.g. 87-95%, with small amounts, e.g., 413% of other phosphates, e.g. pyrophosphate and orthophosphate. Sodium tripolyphosphate in its hydrated form may be used also. Trisodium orthophosphate may be used in the amounts indicated.

The sodium or potassium bicarbonate is an effective pH buffer. The bicarbonate may be incorporated directly as anhydrous bicarbonate or in the form of sesquicarbonate, a hydrate containing both bicarbonate and carbonate.

Other suitable builder salts which may be present include the water-soluble sodium and potassium silicates, carbonates, borates, chlorides and sulfates.

Generally, when present, the builder salt is employed in amount in the range of about 20-90%, preferably at least 25% (e.g. 35 to of the detergent composition.

The composition may also contain polymeric additives such as sodium carboxymethylcellulose or polyvinyl alcohol (e.g. in amount of about 0.15%) or other polymeric additives to inhibit redeposition of soil. Minor amounts of optical brighteners may be present, as in proportions in the range of about 0.01 to 0.15%; examples of such brighteners are the stilbene brighteners such as sodium-2- sulfo 4 (2-naphtho-1,2-triazole) stilbene; disodium 4,4 -bis (4-anilino-6-morpholino s triazin-Z-yl-amino) stilbene disulfonate or disodium 4,4 -bis (4,6-dianilino-striazin-Z-yl-a-mino) stilbene disulfonate; and the oxazole brighteners, having for example a l-phenyl-Z-benzoxazole ethylene structure. Perfumes, coloring agents and preservatives may also be included.

In accordance with certain preferred aspects of this invention, there is also included in the washing detergent composition a minor amount of water-soluble copper salt such as copper sulfate or other highly, soluble inorganic copper salts such as the nitrate or acetate. When such salts are present particularly in such amounts that the detergent composition contains about 20 to 4000 parts of copper atom per million parts of detergent composition (that is, about 0.1 to 20 p.p.m. in a typical 5 g./l. in use solution of the detergent composition) the cleaning efficiency at the boil is markedly increased. A preferred amount of copper salt provides about 10-200 p.p.m. of copper to the detergent composition (that is, about 05-10 p.p.m. in a typical 5 g./ l. in use solution).

In accordance with additional preferred aspects of this invention the cleaning efficiency is further augmented when a minor amount of water-soluble copper salt is present when a sequestering agent is also present in such amount that for each atom of copper, about 0.05-10 molecules, and preferably about 0.1-5 molecules of sequestering agent are present. When the washing detergent composition includes a builder, the sequestering agent may comprise a portion of the builder in admixture with additional salts such as sodium tripolyphosphate.

The sequestering agent when employed in accordance with this aspect of the invention is stable in the presence of the organic peroxide and typically forms a complex with copper having a dissociation constant, the common logarithm of which is between about 11 and -22. Illustrative of the sequestering agents which form such complexes with copper are methylaminodiacetic acid, nitrilotriacetic acid (NTA), also called amino triacetic acid, hydroxyethylaminodiacetic acid, ethylenediamine tetraacetic acid (EDTA) and diethylenetriamine pentaacetic acid (DTPA) and their Water soluble salts. These agents form complexes with copper having the following dissociation constants expressed in -logarithms.

Dissociation constant Agent: of copper complexes Methylaminodiacetic acid 11.09 Nitrilotn'acetic acid 12.68 Hydroxyethylaminodiacetic acid 11.90 Ethylenediamine tetraacetic acid 18.5 Diethylenetriamine pentaacctic acid 21.3

The washing detergent composition of this invention can have the following general formulation by weight:

Surface active agent (i.e. synthetic detergent, soap or mixture thereof): 4-95% Mineral salts (including builder and non-builder salts):

-90% and typically 20-90% Alkali salt of hydroperoxide: -10% Water soluble copper salt: 0% or .0020.4%, Le. 20-

4000 p.p.m. of copper Sequestering agent which forms a copper complex having a dissociation constant the common logarithm of which is between 11 and --22: 0% or 0.05 to molecules for each atom of copper Perfume, colorant, bluing agent, soil antiredeposition agent, etc.: 0-1% The compositions of this invention can be prepared in any suitable manner such as, e.g. by spray drying the surface active agent, mineral salt if present, and copper salt if present, and then adding, by dry mixture, the organic peroxide and, if present, the sequestering agent. Constituents which are sensitive to heat, such as perfume, are also added at this time.

.6 The following examples are given to further illustrate this invention. In these examples, as in the rest of the application, all proportions are by weight unless otherwise indicated.

EXAMPLE 1 Detergent compositions have been prepared each containing a different alkali salt of hydroperoxide and answering to the following general formulation:

Composition I: Percent Sodium dodecyl benzene sulfonate 28 Sodium tripolyphosphate 34 Sodium silicate 6 Salt of sodium hydroperoxide: q.s. for 1% of active oxygen in Composition I. Various products: colorant, perfume, sodium sulfate, soil, antiredeposition agent, moisture: q.s. for

The following results have been obtained:

Percent Alkali salts of hydroperoxide in Composition I EB Sodium salt of cumene hydroperoxide 41 Sodium salt of paramenthane hydroperoxide 33 Potassium salt of tertiobutyl hydroperoxide 15 It is therefore evident that the alkali salts of hydroperoxide are efficient cleaning agents and that particularly advantageous results are obtained by using a sodium salt of the hydroperoxide of cumene.

EXAMPLE 2 In the composition defined in Example 1, but to which different copper levels are added, sodium salt of hydroperoxides (corresponding to 0.4% active oxygen in the composition) and dyed swatches are introduced in the 5 g./l. detergent solutions at the boil as in Example 1.

Cleaning efliciencies of sodium salts of cumene hydroperoxide (C.H.P.) and diisopropylbenzene hydroperoxide (D.I.P.B.H.) expressed as in Example 1, but for a 30- minute wash at the boil are given in Table I below:

TABLE I Cu (p.p.m.)

Compound 0 1 5 10 C.H.P 13 38 67 64 D.I.P.B.H.P 11 36 52 60 It clearly appears that compositions containing copper give higher cleaning efficiencies.

7 EXAMPLE 3 To 85 parts by weight of the following nonfoaming Composition II:

(a) 15 parts by weight of sodium perborate tetrahydrate in order to obtain Composition III which contains 1.5% of active oxygen;

(b) 6.5 parts by weight of sodium salt of the cumene hydroperoxide (B) (of 6.25% active oxygen) and 8.5 parts by weight of sodium sulfate in order to obtain Composition IV which then contains 0.4% of active oxygen (or about four times less than Composition III).

Two batches as similar as possible of soiled household laundry are washedone with Composition III and the other with Composition IV, in a Starline (Lincoln) washing machine following a classical washing cycle (5 g./l. of detergent composition prewashed at 40 C. for ten minutes, washing to boiling maintained for ten minutes).

The washed pieces of each batch are subjected to a visual examination, and the results of this examination expressed by means of a cipher code.

Twelve comparative washings are operated with this pair of detergent compositions and the results of twelve pairs of washings are statistically interpreted. According to the aggregate of twelve pairs of washings, it is found that-Composition 1V containing the alkali salt of hydro peroxide washed as well as Composition HI containing perborate tetrahydrate.

It likewise becomes evident during these washings by introducing squares of cotton dyed with pyrogene black at the same time as the laundry, that Composition IV cleaned just as well as Composition III although it contains four times less active oxygen.

EXAMPLE 4 There is added to 93.5 parts in weight of each of the following Composition V and VI.

Percent Composition. V VI Sodium dodecylbenzene sulfonate 3 3 Sodium tripoly hate 35 35 Sodium silicate 6 6 Tallow soap (sodium salt) 6 6 Oleic acid (E 14.5:l) 6 Cop r sulfate H10 0.4 NT (sodium salt) 0. 04 Minor ingredients (sodium sulfate balance to 100 8 EXAMPLE 5 The tests described in Examples 3 and 4 are duplicated but by using another washing technique (in washing device with 5 g./l. of detergent composition-one night soaking-followed by washing for one hour of which about thirty minutes is at boiling) and by using Composition IX and X adapted to this type of washiim and obtained as follows:

To parts by weight of the following composition:

Percent Sodium alkyl aryl sulfonate 25 Sodium tripolyphosphate 33 Sodium silicate 7 Various products q.s. for

are added:

Percent Composition IV X Losses of active oxygen:

1 month 2 2 months. 4 4 3 months 5 It can be therefore seen that the compositions according to the invention are perfectly stable.

It will be apparent to one skilled in the art that various modifications of the above examples may be made thereto.

What is claimed is:

1. A stable, substantially dry, washing detergent composition for cleaning soiled laundry at the boil which consists essentially of about 4-95% by weight of a watersoluble synthetic surface active agent selected from the group consisting of anionic, nonionic and cationic surface active agents and about 05-10% by weight of an alkali salt of a hydroperoxide having the formula:

in which R R and R are each selected from the group consisting of hydrogen, straight or branched chain alkyl containing 1-12 carbon atoms, cycloalkyl and aromatic radicals, R R and R not being all simultaneously hydrogen and two of R R, and R, capable of being part of the same cyclic hydrocarbon group and M is an alkali metal.

2. The stable substantially dry, washing detergent composition claimed in claim 1 wherein said surface active agent is anionic.

3. The stable substantially dry, washing detergent composition claimed in claim 1 wherein said surface active agent is nonionic.

4. The stable substantially dry, washing detergent composition claimed in claim 1 wherein said detergent composition includes about 20-90% by weight of a watersoluble inorganic builder salt.

5. The stable, substantially dry, washin detergent composition claimed in claim 1 wherein said alkali salt is 9 a salt of the hydroperoxide of cumene, p-menthane or t-butyl.

6. The stable, substantially dry, washing detergent composition claimed in claim 1 wherein said detergent composition includes a water soluble copper salt in such amount that the copper atom content of said detergent composition is about 20-4000 p.p.m.

7. The stable, substantially dry, washing detergent composition claimed in claim 6 wherein said detergent composition includes a water-soluble organic sequestering agent in such amount that for each atom of copper, about 0.05--10 molecules of sequestering agent are present.

References Cited UNITED STATES PATENTS MAYER WEINBLATT, Primary Examiner US. Cl. X.R. 

